Water-insoluble azo-dyestuffs and fiber dyed therewith



Patented Och 3, 1933 Q .t v UNITED STATES PATENT OFFICE WATER INSOLUBLEAZO-DYESTUFFS AND FIBER DYE!) THEREWITH. Fritz Miiller,Frankfort-on-the-Main-Nied, Germany N Drawing. Application April 5,1933, Serial No. 664,669, and in Germany April 12, 1932' Glenn's. (01.260-95) The present invention relates to water-insol- 5oftl1e norms forKochechtheit of the'beforeuble si -dy s u s l o fi r dy d w h; mentionedEchtheitskommission (Schultz, Farbmore particularly it relates tocompounds; of the t fit b u 1, 1, 1931, page XXXII) following generalfOrmlllaI The dyestuffs may be produced in substance,

invention, but they. are not-intended to limit it theretojthe partsbeing by weight unless otherwise stated: I COl\ HR Dyeing prescriptionfor'Eramplesl to 6:, 1 wherein R represents a'radi'cal or" the benzeneor 50 i cottgn yam are treated wlth th naphthalene Series 7 groundingliquor for half-an-hour, squeezed, de- U. S. patent application SerialNo. 5G7,132,'i for hournl the dIaZQiSOIHtKm; 75 filed October 5.1931, inthe name of Erwin lioffa the'dyed a 1s rmsfadi at bollmg and FritzMuller, relates to water-insoluble azoperatul'ea rmsedg agajm afineddyestuiis which are obtainable by coupling the (a) Groundingliquor: diazo-compounds of aminosubstitution products A paste isPrepared from adapted for the production of lakes. I H I a l 1 Thefollowing examples serve'to illustrate the of benzotrifluoride andderivatives thereof with grams of 2.3-hyd ynap oylam n m so 2.3-hydroxynaphthoicacid arylides provided that zene, neither componentcontains any solubilizing 10 Of Turkey red Oil o 0% Strength group, Thetechnical value of these new dyeand I V stuffs resides in the fact thatthey yield orange OfCaU-StiC a SCH-E1011 34" q 2.5 ,dyeings of fastnessproperties such as couldnot be it is, dissolved in boiling waterobtained, hitherto, in the preparation of orange aftefCOOling, p vdyeings by means of 2.3-hydroxynaphthoic acid 5 Of f01ma1dehyde olut ono 33% arylides, strength are addedand the whole According to the presentinvention, there are is e p to on the fiber or on any of the usualsubstrata 65;

30 obtained orange dyeings 01 a more yellow hue by I 90..

using as diazo component the diazo compound of 1000' 9 such-asubstitution product of amino-benzotri- (b) Dwzo solution: fluoride(trifiuoromethylbenzene) as contains one grams 9: i bls 'l iq 3 more orfurther trifiuoromethyl groups and, be- 35 y -enzene f lazo sides, maybe substituted by any substituent, but 4 5 Cc ofrh drochldric acid of200 nd does not contain any solubilizing group, such as of :g nitritesbluti'bn f the sulfonic or carboxylic acid group. By intro- V A ducingone or more trifluoroinethyl groups into dlazo-solutlonls. neutmhzed 49the nucleus of thebenzotrifiuoride, the colour w1th g l scale isextended to such a degree to the yellow 1 gram Q W blcarbonate a side ofthe spectrum as it has, hitherto, not been 10 grams of acetate andiafter d possible by means of arylides of 2.3-hydroxy- (11,1510?! 9 wnaphthoic acid 7 r 25 7 grams of sodium chlorlde, the whole 1s 45 Theiastness to light of the dyeings when pro: I 7' I made up to .105. ducedon cotton is in general, but especially'in the case of the dyestuffsprepared from 1arnino- 9. P 1 3.5-bis-trifluoromethyl benzene, a goodone. In A i yellow 1511 Orange, i good fastness prop the case of thebefore-mentioned base it lies beertles Obtamed- 50 tween grades 5 and 7of the norms for Liam The dyestuffcorresponds to-the followingfortechtheit of the Echtheitskommission der Fachmum? 1 Y a I gruppe fiirChemie der Farbenund Textilindus- 1 c trie im Verein Deutscher Chemiker,4th edit, V l" V 55 1928 (reprinted in Schultz, Farbstofftabellen, 7th 7O edit, vol. 1, 1931, page XXXI et seq).

Furthermore, it is noticeable that the new dyestufis possess a ratherhigh fastness to boiling with Water and to washing. Their fastness in 60this respect lies, in general, between grades 4 and l I T F Q '7 (2)(a), Grounding liquor: 1

grams of 1-(2'3'-hydroxynaphthoylami- 110-) 3-nitrobenzene,

strength.

. (b) Diazo solution:

The diazo solution is prepared as that described in Example 1. A goldenorange is thus obtained. (3) (a) Grounding liquor:

5 grams of 1-(2'3'-hydroxynaphthoylami- (b) Diazo'solution.

The diazo solution is prepared as that described in Example 1. A vividorange is obtained.

(7) Into a diazo solution, prepared from 22.9

parts of l-amino-3.5-bis-trifluoromethylbenzene,

there is graduallyrun, while well stirring, a solution prepared bydissolving 26.3 parts of 2.3- hydroxynaphthoylarninobenzene in causticsoda solution, to which there has been added the quantity of sodiumacetate necessary for binding the excess of mineral acid. When theformation of the'dyestufi is finished, the latter is separated'byfiltrationand washed well. The dyestuff is adv noQ2-1nethoxybenze1 e,vantageously used in the form of a paste. In '10, cc. of Turkey red oilof 50% strength, admixture with one of the usual substrata, it t 7.5 cc.of caustic soda solution of 34 B. yiel an o nge c l r l k f v ry goodfastness properties. s 1000 'cc.; The following dyestuffs, among others,are 0' 5. cc. of formaldehyde solution of 33% capable of production inaccordance with this strength. invention:

Diazo compound of Coupling component Shade l l-amino-.5-bis-tri-flu0romethy1benrene l(23-hydroxyriaphthoylaminm)2-ethoxybenzene. Yellow-orange 2Lamina-2.fi-bis-tri-fiuoromethylbenzenel-(23-hydroxynaphthoylamino-)2-n1etl1oxybenzene Orange 31-an1ino-2.5-bis-tri-fluoromethylbenzene-1-(2'3-l1ydroxynaphthoylan1ino-)4-methoxybenzene Orange-yellow 4'-Lamina-2.5-bis-tri-fluoromethylbenzene..2.3-hydroxynaphthoylaminobenzene Orange 5l-amino-2.5-bis-tri-fluoromethylbenzene1-(2(3-hydroxynaphthoylamino-)4-chlorobenzen Orange-yellow- 6l-aminc-2.5-bis-trifluorornethylbenzeneh;2-(23-hydroxynaphthoylamino-)naphthalene. Orange 7'l-alnin0-3.5-bis-tri-fluoromethylbenzene1-(23-hydroxynaphthoylamino-)2-methylbenzene. Orange-yellow 3C]' 8Lamina-3.5-bis-tri-fluoromethylbenzene.2-(23-hydroxynaphthoylamino-)naphthalene Orange 0-l-amino-3.5-bis-tri-fluoromethylbenzene1-(23-hydroxynaphthoylamino-)4-methylbenzene- Orange 101-amino-3.5-bis-tri-fluoromethylbenzene 1-g3-hydroxynaphthoylamino)2-methyl-4-methoxy- Orange r enzene lll-amino-3.5-bis-tri-fluoromethylbenzenel-(23ghydroxynaphthoylamino-)4-chloro-2.5-dimeth- Orange oxy enzene 121-amino-3.5-bis-tri-fluor0methylbenzene1-(2'3-hydroxynaphthoylamono-)2-ethoxybenzene Orange 13 l-amino-3.5-bistri-fluoromethylbenzene-1-(2'3-hydroxynaphthoylan1ino-)4-1nethoxybenzene Orange 141-amino-3.5-bis-tri-fluoromethylbenzenel-g3-hydroxynaphthoylan1ino-)2-methoxy-4-chlor-Orange enzene (b) Diazo solution:

The diazo solution is prepared'as that described in Example 1; A vivid,yellowish orange is obtained. (4) (a) Grounding liquor:

2 grams of 1-(2'3-hydroxynaphthoylamino-) naphthalene;

10 cc. of Turkey red oil of strength, 6 cc. of caustic soda solution of34 B.,

1000 ca; i 2 cc. of formaldehyde solution of 33% strength.

(b) Diazo solution:-

The diazo solution is prepared as that described in Example 1. A vivid,reddish orange is thus obtained.

-(5) (a) Grounding liquor:

3 grams of 1 (2'3-hydroxynaphthoylami no-) 2-methyl-4 -chlorobenzene,

10 cc. of Turkey red oil of 50% strength, 7.5 cc. of caustic sodasolution of 34 B.,

3 cc. of formaldehyde solution of 33% strength. (b) Diazo solution: 1'The diazo solution is prepared as that described in Example 1. A vividorange is obtained. (6) (a) Grounding liquor:

3 grams of 1-(2'3'-hydroxynaphthoylami- 7 no-) 4-chlorobenzene, 10 cc.of Turkey red oil of 50% strength, 7.5 cc. of caustic soda solution of34 B.;

3 cc. of formaldehyde solution of 33% strength.

Since an object of the present invention is to provide dyestufis of goodfastness' properties, which dyestuffs are insoluble in water and a1-kalies, it is to be understood that the aromatic nuclei of the generalformula appearing in the appended claims do not contain any substituentswhich are known to render organic compounds soluble in water or alkaliesand to tend to depreciate. the fastness of the dyestuffs to alkalies.

' Substituents of this kind are, for instance, the

sulfonic acid and the carboxylic acid group.

I claim: 1. The water-insoluble azo-dyestuffs of the following generalformula: Y

(IJFa wherein R represents, a radical of the benzene or naphthaleneseries, dyeing, in general, yellow-j ish orange shades and beingdistinguished by their good fastness properties, particularly by"- CF3OH 7 dyeing a vivid yellowish-orange shade-and being distinguished byits good fastness properties, particularly by its good fastness tolight.

4. The water-insoluble azo-dyestufi of the following formula:

dyeing an orange shade and being distinguished by its good fastnessproperties, particularly by its good fastness to light. r V g 5. TheWater-insoluble azo-dyestuff of the following formula: 7

( OFa O H Ha C O dyeing a vivid orange shade and being distinguished byits good fastness properties, particularly by its good fastness tolight.

6. Fiber dyed with the azo-dyestuffs as'claimed in claim 1. p

7. Fiber dyed with the azo-dyestufis as claimed in claim 2.

8. Fiber dyed with the azo-dyestuff as claimed in claim 3. i

9. Fiber dyed with the'azo-dyestufi as claimed in claim 4.

10. Fiber dyed with the azo-dyestuff as claimed in claim 5. v

FRITZ MiiLLER.

